Molecular and Supramolecular Structures of Triiodides and Polyiodobismuthates of Phenylenediammonium and Its N,N-dimethyl Derivative

Abstract

Despite remarkable progress in photoconversion efficiency, the toxicity of lead-based hybrid perovskites remains an important issue hindering their applications in consumer optoelectronic devices, such as solar cells, LED displays, and photodetectors. For that reason, lead-free metal halide complexes have attracted great attention as alternative optoelectronic materials. In this work, we demonstrate that reactions of two aromatic diamines with iodine in hydroiodic acid produced phenylenediammonium (PDA) and N,N-dimethyl-phenylenediammonium (DMPDA) triiodides, PDA(I3)2·2H2O and DMPDA(I3)I, respectively. If the source of bismuth was added, they were converted into previously reported PDA(BiI4)2·I2 and new (DMPDA)2(BiI6)(I3)·2H2O, having band gaps of 1.45 and 1.7 eV, respectively, which are in the optimal range for efficient solar light absorbers. All four compounds presented organic–inorganic hybrids, whose supramolecular structures were based on a variety of intermolecular forces, including (N)H⋯I and (N)H⋯O hydrogen bonds as well as I⋯I secondary and weak interactions. Details of their molecular and supramolecular structures are discussed based on single-crystal X-ray diffraction data, thermal analysis, and Raman and optical spectroscopy.

Antimicrobial V-Shaped Copper(II) Pentaiodide: Insights to Bonding Pattern and Susceptibility

“…The attachment of iodine (I 2 ) molecules to the stable triiodide I 3 − ions (I 3 − ) by halogen and hydrogen bonding leads to a variety of polyiodide structures [ 38 , 39 , 40 ]. Triiodides are the basic topology and are utilized in many applications in different fields [ 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 39 , 40 , 41 , 42 , 43 , 44 , 45 ]. Higher polyiodides can be synthesized depending on complexing/stabilizing agents, solvents, and available counterions [ 38 , 39 , 40 ].…”

Molecular self-assembly of 1D linear and 2D T-shape polyiodide arrangements in two organic ammonium triiodide salts: supramolecular structures and density functional theory-based optical properties

“…Compound 1 shows a structured Raman spectrum, where the strongest band observed at 114 cm −1 can be ascribed to the symmetric stretching (ν 1 ) of the anion. 43–45 This vibration (ν 1 ) is typical for all triiodide anions and is supplemented by two weak overtones at 231 cm −1 and 344 cm −1 which are attributed to the 2ν 1 and 3ν 1 vibrational modes. The bands at about 83 cm −1 and 135 cm −1 can be attributed to the bending modes (ν 2 ) and asymmetric stretching vibration (ν 3 ), respectively.…”

Pattern of covalent and non‐covalent interactions within the pentaiodide anion in the structure of (3‐HOC5H9NH2)I5

“…[3,4] Consequently, polyiodides have become the focus of many studies, with particular emphasis being made on the exploratory synthesis, thermodynamic properties, and bonding. [5][6][7][8][9][10][11][12] Importantly, low-melting polyiodides are being used as a medium for converting lead or other post-transition metals into iodometallates. On one hand, this provides a facile way to light-harvesting materials and devices; on the other hand, it requires information on chemistry of polyiodides, including their reactivity that depends largely on the details of chemical bonding within a polyiodide anion.…”

“…The development of a facile polyiodide route to the preparation of iodometallates, first of all iodoplumbates, has led to the development of the polyiodide chemistry [3,4] . Consequently, polyiodides have become the focus of many studies, with particular emphasis being made on the exploratory synthesis, thermodynamic properties, and bonding [5–12] . Importantly, low‐melting polyiodides are being used as a medium for converting lead or other post‐transition metals into iodometallates.…”